US4781814AExpiredUtility
Molecular sieve compositions and their use in cracking/hydrocracking
Est. expiryApr 13, 2004(expired)· nominal 20-yr term from priority
C07C 5/41C07C 2529/84C07C 5/02B01J 29/84C07C 2/54C01B 37/06C07C 5/2716C07C 2/12C07C 5/224C07C 2527/173
69
PatentIndex Score
9
Cited by
2
References
6
Claims
Abstract
Crystalline molecular sieves having three-dimensional microporous framework structure of MO2, AlO2, and PO2 tetrahedral oxide units are disclosed. These molecular sieves have an empirical chemical composition on an anhydrous basis are expressed by the formula: mR: (MxAlyPz)O2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (MxAlyPz)O2; "M" represents at least two elements capable of forming framework tetrahedral oxides and selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides. Their use as adsorbents, catalysts, etc. is disclosed. The catalyst is useful in the cracking and hydrocracking of various hydrocarbonaceous feeds.
Claims
exact text as granted — not AI-modifiedWe claim:
1. Process for cracking a hydrocarbon, which process comprises contacting said hydrocarbon under cracking conditions with a crystalline molecular sieve having three-dimensional microporous framework structures of MO 2 , AlO 2 and PO 2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3; "M" represents at least two elements, M 1 and M 2 , selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of M (=M 1 +M 2 etc.), aluminum and phosphorus, respectively, present as tetrahedral oxides, said mole fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1 and each mole fraction for M 1 , M 2 , aluminum and phosphorus has a value of at least 0.01.
2. Process according to claim 1 wherein, in the crystalline molecular sieve, the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides are such that they are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG. 2.
3. process according to claim 1 wherein the crystalline molecular sieve has a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to H and J to V: TABLE A
______________________________________
(FCAPO-5)
2θ d(Å) Relative Intensity
______________________________________
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
______________________________________
TABLE B
______________________________________
(FCAPO-11)
2θ d(Å) Relative Intensity
______________________________________
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
______________________________________
TABLE C
______________________________________
(FCAPO-14)
2θ d(Å) Relative Intensity
______________________________________
8.6-8.9 10.3-9.93 vs
13.0 6.81 w
21.9-22.2 4.06-4.00 w
25.4 3.51 w
27.5 3.24 w
29.7 3.01 w
______________________________________
TABLE D
______________________________________
(FCAPO-16)
2θ d(Å) Relative Intensity
______________________________________
11.3-11.6 7.83-7.63 m-vs
18.7-18.9 4.75-4.70 w-s
21.9-22.3 4.06-3.99 m-vs
26.5-27.0 3.363-3.302 w-m
29.7-30.05
3.008-2.974 w-m
______________________________________
TABLE E
______________________________________
(FCAPO-17)
2θ d(Å) Relative Intensity
______________________________________
7.7-7.75 11.5-11.4 vs
13.4 6.61 s-vs
15.5-15.55 5.72-5.70 s
19.65-19.7 4.52-4.51 w-s
20.5-20.6 4.33-4.31 vs
31.8-32.00 2.812-2.797 w-s
______________________________________
TABLE F
______________________________________
(FCAPO-18)
2θ d(Å) Relative Intensity
______________________________________
9.6-9.65 9.21-9.16 vs
15.5-15.55
5.72-5.70 m
16.9-17.1 5.25-5.19 m
20.15-20.25
4.41-4.39 m
20.95-21.05
4.24-4.22 m
31.8-32.5 2.814-2.755 m
______________________________________
TABLE G
______________________________________
(FCAPO-20)
2θ d(Å) Relative Intensity
______________________________________
13.7-14.25
6.46-6.22 m-vs
19.55-20.0 4.54-4.44 w-s
24.05-24.5 3.70-3.63 m-vs
34.3-35.0 2.614-2.564 vw-w
42.5-43.0 2.127-2.103 vw-w
______________________________________
TABLE H
______________________________________
(FCAPO-31)
2θ d(Å) Relative Intensity
______________________________________
8.5-8.6 10.40-10.28 m-s
20.2-20.3 4.40-4.37 m
21.9-22.1 4.06-4.02 w-m
22.6-22.7 3.93-3.92 vs
31.7-31.8 2.823-2.814 w-m
______________________________________
TABLE J*
______________________________________
(FCAPO-33)
2θ d(Å) Relative Intensity
______________________________________
9.25-9.55 9.56-9.26 w-m
12.5-12.9 7.08-6.86 vs
16.9-17.3 5.25-5.13 w-m
20.45-20.9 4.34-4.25 w-m
23.85-24.25
3.73-3.67 w-m
26.05-26.35
3.42-3.38 w-m
27.3-27.6 3.27-3.23 vs
______________________________________
*as-synthesized form
TABLE K*
______________________________________
(FCAPO-33)
2θ d(Å) Relative Intensity
______________________________________
13.15-13.4 6.73-6.61 vs
18.05-18.35
4.91-4.83 m
18.4-18.6 4.82-4.77 m
26.55-26.7 3.36-3.34 m
32.0-32.1 2.80-2.79 m
______________________________________
*calcined form
TABLE L
______________________________________
(FCAPO-34)
2θ d(Å) Relative Intensity
______________________________________
9.4-9.65 9.41-9.17 s-vs
15.9-16.2 5.57-5.47 vw-m
17.85-18.4 4.97-4.82 w-s
20.3-20.9 4.37-4.25 m-vs
24.95-25.4 3.57-3.51 vw-s
30.3-30.8 2.95-2.90 w-s
______________________________________
TABLE M
______________________________________
(FCAPO-35)
2θ d(Å) Relative Intensity
______________________________________
10.8-11.1 8.19-7.97 m
17.2-17.4 5.16-5.10 s-vs
21.0-21.25
4.23-4.18 m-s
21.8-22.0 4.08-4.04 vs
31.8-32.2 2.814-2.788 m
______________________________________
TABLE N
______________________________________
(FCAPO-36)
2θ d(Å) Relative Intensity
______________________________________
7.7-7.9 11.5-11.2 vs
16.2-16.6 5.47-5.34 w-m
18.9-19.3 4.70-4.60 m-s
20.6-20.8 4.31-4.27 w-s
21.8-22.0 4.08-4.04 m
22.2-22.5 4.00-3.95 w-m
______________________________________
TABLE O
______________________________________
(FCAPO-37)
2θ d(Å) Relative Intensity
______________________________________
6.1-6.3 14.49-14.03 vs
15.5-15.7 5.72-5.64 w-m
18.5-18.8 4.80-4.72 w-m
23.5-23.7 3.79-3.75 w-m
26.9-27.1 3.31-3.29 w-m
______________________________________
TABLE P
______________________________________
(FCAPO-39)
2θ d(Å) Relative Intensity
______________________________________
9.4-9.6 9.41-9.21 w-m
13.3-13.6 6.66-6.51 m-vs
18.0-18.4 4.93-4.82 m
21.2-21.5 4.19-4.13 m-s
22.5-23.0 3.95-3.87 s-vs
30.2-30.5 2.96-2.93 w-m
______________________________________
TABLE Q
______________________________________
(FCAPO-40)
2θ d(Å) Relative Intensity
______________________________________
7.5-7.7 11.79-11.48 vw-m
8.0-8.1 11.05-10.94 s-vs
12.4-12.5 7.14-7.08 w-vs
13.6-13.8 6.51-6.42 m-s
14.0-14.1 6.33-6.28 w-m
27.8-28.0 3.209-3.187 w-m
______________________________________
TABLE R
______________________________________
(FCAPO-41)
2θ d(Å) Relative Intensity
______________________________________
13.6-13.8 6.51-6.42 w-m
20.5-20.6 4.33-4.31 w-m
21.1-21.3 4.21-4.17 vs
22.1-22.3 4.02-3.99 m-s
22.8-23.0 3.90-3.86 m
23.1-23.4 3.82-3.80 w-m
25.5-25.9 3.493-3.440 w-m
______________________________________
TABLE S
______________________________________
(FCAPO-42)
2θ d(Å) Relative Intensity
______________________________________
7.15-7.4 12.36-11.95 m-vs
12.5-12.7 7.08-6.97 m-s
21.75-21.9 4.09-4.06 m-s
24.1-24.25
3.69-3.67 vs
27.25-27.4 3.273-3.255 s
30.05-30.25
2.974-2.955 m-s
______________________________________
TABLE T
______________________________________
(FCAPO-44)
2θ d(Å) Relative Intensity
______________________________________
9.4-9.55 9.41-9.26 vs
13.0-13.1 6.81-6.76 w-m
16.0-16.2 5.54-5.47 w-m
20.6-20.85
4.31-4.26 s-vs
24.3-24.4 3.66-3.65 w-vs
30.7-30.95
2.912-2.889 w-s
______________________________________
TABLE U
______________________________________
(FCAPO-46)
2θ d(Å) Relative Intensity
______________________________________
7.2-8.1 12.3-10.9 vs
21.2-21.8 4.19-4.08 w-m
22.5-23.0 3.95-3.87 vw-m
26.6-27.2 3.351-3.278 vw-w
28.5-29.0 3.132-3.079 vw-w
______________________________________
TABLE V
______________________________________
(FCAPO-47)
2θ d(Å) Relative Intensity
______________________________________
9.4 9.41 vs
15.9-16.0 5.57-5.54 w-m
20.5-20.6 4.33-4.31 s
24.5-24.7 3.63-3.60 w
25.8-25.9 3.45-3.44 w
30.4-30.5 2.940-2.931 w.
______________________________________
4. Process for hydrocracking a hydrocarbon, which process comprises contacting said hydrocarbon under hydrocracking conditions with a crystalline molecular sieve having three-dimensional microporous framework structures of MO 2 , AlO 2 and PO 2 tetrahedral units and having an empirical chemical composition on an anhydrous basis expressed by the formula: mR:(M.sub.x Al.sub.y P.sub.z)O.sub.2 wherein "R" represents at least one organic templating agent present in the intracrystalline pore system; "m" represents the molar amount of "R" present per mole of (M x Al y P z )O 2 and has a value of zero to about 0.3; "M" represents at least two elements, M 1 and M 2 , selected from the group consisting of arsenic, beryllium, boron, chromium, gallium, germanium, lithium and vanadium; and "x", "y" and "z" represent the mole fractions of M (=M 1 +M 2 etc.)., aluminum and phosphorus, respectively, present as tetrahedral oxides, said moles fractions being such that they are within the pentagonal compositional area defined by points A, B, C, D and E of FIG. 1 and each mole fraction for M 1 , M 2 , aluminum and phosphorus has a value of at least 0.01.
5. Process according to claim 4 wherein, in the crystalline molecular sieve, the mole fractions of "M", aluminum and phosphorus, respectively, present as tetrahedral oxides are such that they are within the hexagonal compositional area defined by points a, b, c, d, e and f of FIG. 2.
6. Process according to claim 4 wherein the crystalline molecular sieve has a characteristic X-ray powder diffraction pattern which contains at least the d-spacings set forth in one of the following Tables A to H and J to V: TABLE A
______________________________________
(FCAPO-5)
2θ d(Å) Relative Intensity
______________________________________
7.3-7.65 12.1-11.56 m-vs
19.5-19.95 4.55-4.46 m-s
20.9-21.3 4.25-4.17 m-vs
22.2-22.6 4.00-3.93 w-vs
25.7-26.15 3.47-3.40 w-m
______________________________________
TABLE B
______________________________________
(FCAPO-11)
2θ d(Å) Relative Intensity
______________________________________
9.3-9.65 9.51-9.17 m-s
20.2-20.6 4.40-4.31 m-s
20.9-21.3 4.25-4.17 s-vs
22.0-22.5 4.04-3.95 m-s
22.5-22.9 3.95-3.92 m-s
23.0-23.4 3.87-3.80 m-vs
______________________________________
TABLE C
______________________________________
(FCAPO-14)
2θ d(Å) Relative Intensity
______________________________________
8.6-8.9 10.3-9.93 vs
13.0 6.81 w
21.9-22.2 4.06-4.00 w
25.4 3.51 w
27.5 3.24 w
29.7 3.01 w
______________________________________
TABLE D
______________________________________
(FCAPO-16)
2θ d(Å) Relative Intensity
______________________________________
11.3-11.6 7.83-7.63 m-vs
18.7-18.9 4.75-4.70 w-s
21.9-22.3 4.06-3.99 m-vs
26.5-27.0 3.363-3.302 w-m
29.7-30.05
3.008-2.974 w-m
______________________________________
TABLE E
______________________________________
(FCAPO-17)
2θ d(Å) Relative Intensity
______________________________________
7.7-7.75 11.5-11.4 vs
13.4 6.61 s-vs
15.5-15.55 5.72-5.70 s
19.65-19.7 4.52-4.51 w-s
20.5-20.6 4.33-4.31 vs
31.8-32.00 2.812-2.797 w-s
______________________________________
TABLE F
______________________________________
(FCAPO-18)
2θ d(Å) Relative Intensity
______________________________________
9.6-9.65 9.21-9.16 vs
15.5-15.55
5.72-5.70 m
16.9-17.1 5.25-5.19 m
20.15-20.25
4.41-4.39 m
20.95-21.05
4.24-4.22 m
31.8-32.5 2.814-2.755 m
______________________________________
TABLE G
______________________________________
(FCAPO-20)
2θ d(Å) Relative Intensity
______________________________________
13.7-14.25
6.46-6.22 m-vs
19.55-20.0 4.54-4.44 w-s
24.05-24.5 3.70-3.63 m-vs
34.3-35.0 2.614-2.564 vw-w
42.5-43.0 2.127-2.103 vw-w
______________________________________
TABLE H
______________________________________
(FCAPO-31)
2θ d(Å) Relative Intensity
______________________________________
8.5-8.6 10.40-10.28 m-s
20.2-20.3 4.40-4.37 m
21.9-22.1 4.06-4.02 w-m
22.6-22.7 3.93-3.92 vs
31.7-31.8 2.823-2.814 w-m
______________________________________
TABLE J*
______________________________________
(FCAPO-33)
2θ d(Å) Relative Intensity
______________________________________
9.25-9.55 9.56-9.26 w-m
12.5-12.9 7.08-6.86 vs
16.9-17.3 5.25-5.13 w-m
20.45-20.9 4.34-4.25 w-m
23.85-24.25
3.73-3.67 w-m
26.05-26.35
3.42-3.38 w-m
27.3-27.6 3.27-3.23 vs
______________________________________
*as-synthesized form
TABLE K*
______________________________________
(FCAPO-33)
2θ d(Å) Relative Intensity
______________________________________
13.15-13.4 6.73-6.61 vs
18.05-18.35
4.91-4.83 m
18.4-18.6 4.82-4.77 m
26.55-26.7 3.36-3.34 m
32.0-32.1 2.80-2.79 m
______________________________________
*calcined form
TABLE L
______________________________________
(FCAPO-34)
2θ d(Å) Relative Intensity
______________________________________
9.4-9.65 9.41-9.17 s-vs
15.9-16.2 5.57-5.47 vw-m
17.85-18.4 4.97-4.82 w-s
20.3-20.9 4.37-4.25 m-vs
24.95-25.4 3.57-3.51 vw-s
30.3-30.8 2.95-2.90 w-s
______________________________________
TABLE M
______________________________________
(FCAPO-35)
2θ d(Å) Relative Intensity
______________________________________
10.8-11.1 8.19-7.97 m
17.2-17.4 5.16-5.10 s-vs
21.0-21.25
4.23-4.18 m-s
21.8-22.0 4.08-4.04 vs
31.8-32.2 2.814-2.788 m
______________________________________
TABLE N
______________________________________
(FCAPO-36)
2θ d(Å) Relative Intensity
______________________________________
7.7-7.9 11.5-11.2 vs
16.2-16.6 5.47-5.34 w-m
18.9-19.3 4.70-4.60 m-s
20.6-20.8 4.31-4.27 w-s
21.8-22.0 4.08-4.04 m
22.2-22.5 4.00-3.95 w-m
______________________________________
TABLE O
______________________________________
(FCAPO-37)
2θ d(Å) Relative Intensity
______________________________________
6.1-6.3 14.49-14.03 vs
15.5-15.7 5.72-5.64 w-m
18.5-18.8 4.80-4.72 w-m
23.5-23.7 3.79-3.75 w-m
26.9-27.1 3.31-3.29 w-m
______________________________________
TABLE P
______________________________________
(FCAPO-39)
2θ d(Å) Relative Intensity
______________________________________
9.4-9.6 9.41-9.21 w-m
13.3-13.6 6.66-6.51 m-vs
18.0-18.4 4.93-4.82 m
21.2-21.5 4.19-4.13 m-s
22.5-23.0 3.95-3.87 s-vs
30.2-30.5 2.96-2.93 w-m
______________________________________
TABLE Q
______________________________________
(FCAPO-40)
2θ d(Å) Relative Intensity
______________________________________
7.5-7.7 11.79-11.48 vw-m
8.0-8.1 11.05-10.94 s-vs
12.4-12.5 7.14-7.08 w-vs
13.6-13.8 6.51-6.42 m-s
14.0-14.1 6.33-6.28 w-m
27.8-28.0 3.209-3.187 w-m
______________________________________
TABLE R
______________________________________
(FCAPO-41)
2θ d(Å) Relative Intensity
______________________________________
13.6-13.8 6.51-6.42 w-m
20.5-20.6 4.33-4.31 w-m
21.1-21.3 4.21-4.17 vs
22.1-22.3 4.02-3.99 m-s
22.8-23.0 3.90-3.86 m
23.1-23.4 3.82-3.80 w-m
25.5-25.9 3.493-3.440 w-m
______________________________________
TABLE S
______________________________________
(FCAPO-42)
2θ d(Å) Relative Intensity
______________________________________
7.15-7.4 12.36-11.95 m-vs
12.5-12.7 7.08-6.97 m-s
21.75-21.9 4.09-4.06 m-s
24.1-24.25
3.69-3.67 vs
27.25-27.4 3.273-3.255 s
30.05-30.25
2.974-2.955 m-s
______________________________________
TABLE T
______________________________________
(FCAPO-44)
2θ d(Å) Relative Intensity
______________________________________
9.4-9.55 9.41-9.26 vs
13.0-13.1 6.81-6.76 w-m
16.0-16.2 5.54-5.47 w-m
20.6-20.85
4.31-4.26 s-vs
24.3-24.4 3.66-3.65 w-vs
30.7-30.95
2.912-2.889 w-s
______________________________________
TABLE U
______________________________________
(FCAPO-46)
2θ d(Å) Relative Intensity
______________________________________
7.2-8.1 12.3-10.9 vs
21.2-21.8 4.19-4.08 w-m
22.5-23.0 3.95-3.87 vw-m
26.6-27.2 3.351-3.278 vw-w
28.5-29.0 3.132-3.079 vw-w
______________________________________
TABLE V
______________________________________
(FCAPO-47)
2θ d(Å) Relative Intensity
______________________________________
9.4 9.41 vs
15.9-16.0 5.57-5.54 w-m
20.5-20.6 4.33-4.31 s
24.5-24.7 3.63-3.60 w
25.8-25.9 3.45-3.44 w
30.4-30.5 2.940-2.931 w.
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